EP0846675B1 - Procédé de préparation d'amines à partir d'oléfines utilisant des zéolites des types MCM-49 ou MCM-56 - Google Patents

Procédé de préparation d'amines à partir d'oléfines utilisant des zéolites des types MCM-49 ou MCM-56 Download PDF

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EP0846675B1
EP0846675B1 EP97121047A EP97121047A EP0846675B1 EP 0846675 B1 EP0846675 B1 EP 0846675B1 EP 97121047 A EP97121047 A EP 97121047A EP 97121047 A EP97121047 A EP 97121047A EP 0846675 B1 EP0846675 B1 EP 0846675B1
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mcm
zeolites
type
preparing amines
alkyl
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EP0846675A1 (fr
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Karsten Dr. Eller
Rudolf Dr. Kummer
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/60—Preparation of compounds containing amino groups bound to a carbon skeleton by condensation or addition reactions, e.g. Mannich reaction, addition of ammonia or amines to alkenes or to alkynes or addition of compounds containing an active hydrogen atom to Schiff's bases, quinone imines, or aziranes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • the present invention relates to a method for manufacturing of amines by reacting ammonia or primary or secondary amines with olefins at elevated temperatures and Press in the presence of MCM-49 or MCM-56 zeolites.
  • the olefin will coordinated via a metal complex. This activated species can be attacked by the nucleophilic amine and a higher one form aminated product.
  • the amine can be at acid centers or at Metal centers (via metal amides) are chemisorbed and so activated with the olefin.
  • Zeolites are very suitable catalysts. You stand out by a high number of catalytically active centers combined with a large surface.
  • the described Zeolites differ in type and in the after-treatment (e.g. thermal treatment, dealumination, acid treatment, Metal ion exchange, etc.). Examples of this can be found in US-A-4 375 002, US-A-4 536 602, EP-A-305 564, EP-A-101 921, DE-A-42 06 992.
  • EP-A-133 938 Methods are known from EP-A-133 938, EP-A-431 451 and EP-A-132 736 known in which boron, gallium, alumino and iron silicate zeolites used for the production of amines from olefins and the possibility of doping these zeolites with Alkali, alkaline earth and transition metals is pointed out.
  • CA-A-2 092 964 describes a process for the preparation of amines known from olefins in the BETA zeolites, which are called crystalline Aluminosilicates of a certain composition with a pore size of more than 5 ⁇ are used. Prefers become metal- or halogen-modified beta zeolites used.
  • Catalysts are characterized by a low amine yield or low space-time yield, or lead to one rapid deactivation of the catalysts.
  • the present invention was therefore based on the object to remedy these disadvantages.
  • the method according to the invention can be carried out as follows become:
  • the olefin II and ammonia or the primary or secondary amine III can at temperatures of 200 to 350 ° C, preferably 220 to 330 ° C, particularly preferably 230 to 320 ° C and pressures from 100 to 300 bar, preferably 120 to 300 bar, particularly preferably 140 to 290 bar in the presence of MCM-49 or MCM-56 zeolites as a catalyst e.g. be implemented in a pressure reactor, and preferably the amine obtained and the unreacted Feedstocks are recycled.
  • the present method is characterized by a very good one Yield with high selectivity and with high space-time yield out. In addition, the deactivation of the catalyst been pushed back.
  • the inventive method is characterized in that already high with a low excess of ammonia or amine Selectivity achieved on the desired reaction product and the Dimerization and / or oligomerization of the olefin used is avoided.
  • One embodiment of this method is that Ammonia and / or amines III together with the olefin II in molar ratio of 1: 1 to 5: 1 mixed a fixed bed reactor feeds and at a pressure of 100 to 300 bar and a temperature of 200 to 350 ° C in the gas phase or in implemented supercritical state.
  • the desired product can be extracted from the reaction discharge using known methods, for example distillation or extraction, preserved and if necessary by means of further separation operations the desired purity can be brought.
  • the unconverted Input materials are usually preferred in the reactor returned.
  • thermodynamic View not advantageous.
  • the location of the optimum temperature in relation Turnover and selectivity is dependent on the constitution of the olefin, depending on the amine and the catalyst used and is usually in the range of 200 to 350 ° C.
  • MCM-49 is for example from EP-A-590 078 and MCM-56 from US-A-5 362 697.
  • MCM-49 is a three-dimensional zeolite that has a certain relationship with the two-dimensional MCM-22 zeolite, which from the older German application DE-A-195 26 502 for the Amination of olefins is known.
  • the differentiating Features of the X-ray powder diffractograms are described in J. Phys. Chem. 100 (1996) 3788 to 3798 by Lawton et al. described.
  • MCM-56 belongs to the same zeolite family as in US-A-5 362 697 and US-A-5 453 554. All three zeolites with hexamethyleneimine as a template (structure-building Medium) synthesized so that the close relationship is understandable is.
  • MCM-49 or MCM-56 zeolites are not just pure zeolites of this type but also mixtures thereof and mixtures falling from MCM-49 and / or MCM-56 with MCM-22. Among mixtures these fall not only physical mixtures but also Mixed crystals of the three zeolites MCM-22, MCM-49 and MCM-56.
  • zeolites of the type MCM-49 or MCM-56 with aluminum as a trivalent element in the SiO 2 matrix other elements are also possible within the meaning of this application if acidic centers are created by their installation. This is the case, for example, with boron zeolites, iron zeolites or gallium zeolites.
  • the molar ratio of SiO 2 to the oxides of the trivalent elements, the so-called module SiO 2 / M 2 O 3 (M Al, B, Ga, Fe), can vary from almost infinite to a few tens, depending on the zeolite class. [B] -MCM-49 is described, for example, in Lawton et al., J. Phys. Chem. 100 (1996) 3788 to 3798.
  • silicon can also be isomorphic to be substituted by other tetravalent elements, so for Example by Ge, Ti or Sn.
  • analog structures can also be realized on the basis of aluminum phosphates, the so-called AlPOs. If these contain aluminum and phosphorus in a ratio greater than 1, they are also acidic and can be used for the purposes of the invention. If part of the phosphorus and / or aluminum and phosphorus are simultaneously replaced by silicon, the so-called SAPOs are obtained, which are also acidic.
  • the MCM-49 or MCM-56 zeolites according to the invention can be shaped as such, or else with a binder in a ratio of 98: 2 to 40:60% by weight to extrudates or tablets.
  • Various aluminum oxides preferably boehmite, amorphous aluminosilicates with an SiO 2 / Al 2 O 3 ratio of 25:75 to 95: 5, silicon dioxide, preferably highly disperse SiO 2 , mixtures of highly disperse SiO 2 and highly disperse Al 2 O 3 are suitable as binders , highly disperse TiO 2 and clays.
  • the extrudates or compacts are expediently dried at 110 ° C./16 hours and calcined at 200 to 500 ° C./2 to 16 hours, the calcination also being able to take place directly in the amination reactor.
  • a modification of the catalysts is that the undeformed or the deformed zeolites with alkali metals such as Na and K, alkaline earth metals like Ca, Mg, earth metals like Tl, Transition metals such as Ti, Zr, Mn, Fe, Mo, Cu, Zn, Cr, precious metals and / or rare earth metals such as La, Ce or Y ion exchange or doping.
  • alkali metals such as Na and K
  • alkaline earth metals like Ca
  • Mg earth metals like Tl
  • Transition metals such as Ti, Zr, Mn, Fe, Mo, Cu, Zn, Cr, precious metals and / or rare earth metals such as La, Ce or Y ion exchange or doping.
  • An advantageous embodiment is that one deformed MCM-49 or zeolites according to the invention MCM-56 placed in a flow tube and at 20 to 100 ° C e.g. a halide, an acetate, an oxalate, a citrate or a nitrate of the metals described above in dissolved form directs.
  • ion exchange can e.g. at the hydrogen, Ammonium and alkali form of the zeolites according to the invention MCM-49 or MCM-56.
  • metal-doped zeolites of type MCM-49 or MCM-56 can be post-treated with hydrogen and / or with Water vapor can be cheap.
  • a further possibility for modification consists in that the MCM-49 or MCM-56 zeolites according to the invention - deformed or undeformed - are treated with acids such as hydrochloric acid (HCl), hydrofluoric acid (HF), sulfuric acid (H 2 SO 4 ) , Phosphoric acid (H 3 PO 4 ), oxalic acid (HO 2 C-CO 2 H) or mixtures thereof.
  • acids such as hydrochloric acid (HCl), hydrofluoric acid (HF), sulfuric acid (H 2 SO 4 ) , Phosphoric acid (H 3 PO 4 ), oxalic acid (HO 2 C-CO 2 H) or mixtures thereof.
  • a special embodiment is that one Zeolites of the type MCM-49 or MCM-56 according to the invention before Deformation with one of the acids mentioned 0.001 n to 2 n, preferably 0.05 to 0.5 n 1 to 100 hours under reflux treated. After filtering and washing out is usually dried at 100 to 160 ° C and calcined at 200 to 600 ° C.
  • Another special embodiment is an acid treatment of the MCM-49 or MCM-56 after being deformed with binder.
  • the Zeolite according to the invention generally between 1 and 3 hours 60 and 80 ° C with a 3 to 25%, especially with a 12 treated to 20% acid, then washed out, at 100 dried to 160 ° C and calcined at 200 to 600 ° C.
  • the calcination can be carried out directly in the amination reactor respectively.
  • the zeolite deformed with the binder is generally exchanged continuously at 60 to 80 ° C. with 10 to 25%, preferably 20%, NH 4 Cl solution for 2 hours in a weight-based zeolite / ammonium chloride solution of 1:15 and then at 100 to 120 ° C dried.
  • Another modification that can be made to the zeolites according to the invention is dealumination in the case of aluminum zeolites, in which some of the aluminum atoms are replaced by silicon or the zeolites are depleted in their aluminum content by, for example, hydrothermal treatment.
  • a hydrothermal dealumination advantageously is followed by extraction with acids or complexing agents in order to remove non-lattice aluminum formed.
  • Aluminum can be replaced by silicon, for example using (NH 4 ) 2 SiF 6 or SiCl 4 .
  • Examples of dealuminations of Y zeolites can be found in Corma et al., Stud. Surf. Sci. Catal. 37 (1987), pages 495 to 503.
  • the modulus can be increased accordingly by removing part of the boron, iron or gallium or replacing it with silicon.
  • the catalysts can be used as strands with diameters of e.g. 1 to 4 mm or as tablets with e.g. 3 to 5 mm diameter use for the amination of the olefins.
  • a size of 0.1 is obtained by grinding and sieving received up to 0.8 mm.
  • catalyst A 150 g of catalyst A were stirred with 2250 g of a 20% strength NH 4 Cl solution at 80 ° C. for 2 h and then filtered off and washed with 4 l of water. After renewed NH 4 Cl exchange and washing with 12 l of water, the zeolite was dried at 120 ° C. for 2 hours and calcined at 500 ° C. for 5 hours. The entire process was then repeated again.
  • the sodium analysis showed a value of 0.07%.
  • catalyst C 100 g were stirred with 1500 g of a 20% strength NH 4 Cl solution at 80 ° C. for 2 h and then filtered off and washed with 5 l of water. After renewed NH 4 Cl exchange and washing with 10 l of water, the zeolite was dried at 120 ° C. for 2 hours and calcined at 500 ° C. for 5 hours. The entire process was then repeated again.
  • the sodium analysis showed a value of 0.03%.
  • 60 g of the exchanged zeolite were mixed with 40 g of boehmite and 2 g of formic acid compacted in a kneader and with the addition of water (100 ml) kneaded for 35 min.
  • Catalyst E Na-MCM-49
  • catalyst E 100 g of catalyst E were stirred with 1500 g of a 20% strength NH 4 Cl solution at 80 ° C. for 2 h and then filtered off and washed with 5 l of water. After renewed NH 4 Cl exchange and washing with 10 l of water, the zeolite was dried at 120 ° C. for 2 hours and calcined at 500 ° C. for 5 hours. The entire process was then repeated again.
  • 80 g of the exchanged zeolite were mixed with 53 g of boehmite and 3 g of formic acid compacted in a kneader and with the addition of water (110 ml) kneaded for 60 min.
  • the sodium analysis gave a value of 0.11%.
  • the tests were carried out in a tubular reactor (6 mm inside diameter) under isothermal conditions at 260 to 300 ° C and a pressure of 280 bar with a mixture of isobutene and ammonia in molar ratio of 1: 1.5 performed.
  • the reaction products were analyzed in a gas chromatograph.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Claims (12)

  1. Procédé de préparation d'amines de la formule générale I
    Figure 00180001
       dans laquelle
    R1, R2, R3, R4, R5, R6
    représentent l'hydrogène, ou un radical alkyle en C1 à C20, alcényle en C2 à C20, alkinyle en C2 à C20, cycloalkyle en C3 à C20, alkylcycloalkyle en C4 à C20, cycloalkylalkyle en C4 à C20, aryle, alkylaryle en C7 à C20 ou aralkyle en C7 à C20.
    R1 et R2
    représentent ensemble une double chaíne alkylénique saturée ou insaturée en C3 à C9 et
    R3 ou R5
    représentent un radical alkyle en C21 à C200, ou forment ensemble une double chaíne alkylénique en C2 à C12
       par réaction d'oléfines de la formule générale II
    Figure 00180002
    dans laquelle R3, R4, R5 et R6 ont les significations ci-dessus, avec de l'ammoniac ou des amines primaires ou secondaires de la formule générale III
    Figure 00190001
    dans laquelle R1 et R2 ont les significations ci-dessus, à des températures de 200 à 350°C et des pressions de 100 à 300 bar, en présence d'un catalyseur hétérogène, caractérisé en ce que l'on met en oeuvre, en tant que catalyseur hétérogène, des zéolithes du type MCM-49 ou MCM-56.
  2. Procédé de préparation d'amines I selon la revendication 1, caractérisé en ce que l'amine 1 formée est séparée et que l'on recycle les substances de départ II et III n'ayant pas réagi.
  3. Procédé de préparation d'amines selon les revendications 1 à 2, caractérisé en ce que l'on met en oeuvre, en tant qu'oléfine II, de l'isobutène, du diisobutène, du cyclopentène, du cyclohexène ou du polyisobutène.
  4. Procédé de préparation d'amines selon les revendications 1 à 3, caractérisé en ce que l'on met en oeuvre, en tant que catalyseurs hétérogènes, des zéolithes de type MCM-49 ou MCM-56 sous leur forme H.
  5. Procédé de préparation d'amines selon les revendications 1 à 4, caractérisé en ce que l'on met en oeuvre, en tant que catalyseurs hétérogènes, des zéolithes de type MCM-49 ou MCM-56 après traitement à l'acide, en particulier des acides choisis dans le groupe formé par l'acide chlorhydrique, l'acide fluorhydrique, l'acide sulfurique, l'acide phosphorique, l'acide oxalique ou leurs mélanges.
  6. Procédé de préparation d'amines selon les revendications 1 à 5, caractérisé en ce que l'on met en oeuvre, comme catalyseurs hétérogènes, des zéolithes de type MCM-49 ou MCM-56, dopées par un ou plusieurs métaux de transition.
  7. Procédé de préparation d'amines selon les revendications 1 à 6, caractérisé en ce que l'on met en oeuvre, en tant que catalyseurs hétérogènes, des zéolithes de type MCM-49 ou MCM-56, dopées par un ou plusieurs éléments parmi les terres rares.
  8. Procédé de préparation d'amines selon les revendications 1 à 7, caractérisé en ce que l'on met en oeuvre, en tant que catalyseurs hétérogènes, des zéolithes de type MCM-49 ou MCM-56 sous leur forme ammoniacale.
  9. Procédé de préparation d'amines selon les revendications 1 à 8, caractérisé en ce que l'on met en oeuvre, en tant que catalyseurs hétérogènes, des zéolithes de type MCM-49 ou MCM-56, dopées par un ou plusieurs éléments des groupes des métaux alcalins et alcalino-terreux ou des métaux terreux.
  10. Procédé de préparation d'amines selon les revendications 1 à 9, caractérisé en ce que l'on met en oeuvre, en tant que catalyseurs hétérogènes, des zéolithes de type MCM-49 ou MCM-56 après formage avec un liant et calcination à des températures de 200 à 600°C.
  11. Procédé de préparation d'amines selon les revendications 1 à 9, caractérisé en ce que l'on met en oeuvre, en tant que catalyseurs hétérogènes, des zéolithes de type MCM-49 ou MCM-56 désaluminées ou déborées.
  12. Procédé de préparation d'amines selon les revendications 1 à 8, caractérisé en ce que l'on met en oeuvre, en tant que catalyseurs hétérogènes, une zéolithe [AI]-MCM-49.
EP97121047A 1996-12-03 1997-12-01 Procédé de préparation d'amines à partir d'oléfines utilisant des zéolites des types MCM-49 ou MCM-56 Expired - Lifetime EP0846675B1 (fr)

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DE19649944 1996-12-03
DE19649944A DE19649944A1 (de) 1996-12-03 1996-12-03 Verfahren zur Herstellung von Aminen aus Olefinen an Zeolithen des Typs MCM-49 oder MCM-56

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EP0846675B1 true EP0846675B1 (fr) 2001-03-28

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US6051521A (en) * 1998-08-25 2000-04-18 Mobil Oil Corporation Method of producing an aromatics alkylation catalyst
US6641714B2 (en) 2000-07-21 2003-11-04 Exxonmobil Research And Engineering Company Hydrocarbon upgrading process
US20020042548A1 (en) * 2001-07-11 2002-04-11 Dandekar Ajit B. Process for producing cumene
US8395008B2 (en) 2008-01-14 2013-03-12 Catalytic Distillation Technologies Process and catalyst for cracking of ethers and alcohols

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Publication number Priority date Publication date Assignee Title
US4375002A (en) * 1980-05-09 1983-02-22 Air Products And Chemicals, Inc. Amines via the amination of olefins
MX157137A (es) * 1982-07-30 1988-10-28 Air Prod & Chem Procedimiento mejorado para la obtencion de alquilaminas
DE3326579A1 (de) * 1983-07-23 1985-01-31 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von aminen
DE3327000A1 (de) * 1983-07-27 1985-02-07 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von aminen
US4536602A (en) * 1984-06-01 1985-08-20 Air Products And Chemicals, Inc. Amination of olefins using organic acid catalysts
EP0305564A1 (fr) * 1987-09-01 1989-03-08 Air Products And Chemicals, Inc. Amines par amination d'oléfines avec des zéolites déaluminées
DE3940349A1 (de) * 1989-12-06 1991-06-13 Basf Ag Verfahren zur herstellung von aminen
US5236575A (en) * 1991-06-19 1993-08-17 Mobil Oil Corp. Synthetic porous crystalline mcm-49, its synthesis and use
DE4206992A1 (de) * 1992-03-05 1993-09-09 Akzo Nv Verfahren zur herstellung von tertiaerem butylamin
CA2086814A1 (fr) * 1992-09-08 1994-03-09 Brian L. Benac Synthese de tert-butylamine sur des zeolites de type y desaluminisees
CA2092964A1 (fr) * 1992-12-03 1994-06-04 John Frederick Knifton Synthese de 2-methylpropan-2-amine
US5362697A (en) * 1993-04-26 1994-11-08 Mobil Oil Corp. Synthetic layered MCM-56, its synthesis and use
DE19526502A1 (de) * 1995-07-20 1997-01-23 Basf Ag Verfahren zur Herstellung von Aminen aus Olefinen an Zeolithen des Typs PSH-3, MCM-22, SSZ-35 oder deren Gemischen
DE19615482A1 (de) * 1996-04-19 1997-10-23 Basf Ag Verfahren zur Herstellung von Aminen aus Olefinen an mesoporösen Oxiden mit hoher Oberfläche

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US5840988A (en) 1998-11-24
DE19649944A1 (de) 1998-06-04
DE59703229D1 (de) 2001-05-03
JPH10291968A (ja) 1998-11-04
EP0846675A1 (fr) 1998-06-10
JP4201367B2 (ja) 2008-12-24

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